Quaternary ammonium compounds having a hydroxybutynyl substituent



Patented Jan. 15, 1952 QUA'IERNARY AMMONIUM co oUNDs HAVING A HYDROXYBUTYNYL SPTITUENT Willard J. cmxan, Bryn Athyn,-and Sidney Melamed, Philadelphia, Pa., assignors .toRohnL 54 Ideas Com any; Philadelphia, n co n I ration of Delaware I Nollrawing. Applicationzl'anuary 4, 1.951 1,"

Serial No. 204,481

'1 Claims. (01. 26.015626) This invention deals with quaternary ammonium compounds of the formula derived from a close-cut kerosene traction, one

having a content of about 14' carbon atoms being particularly useful.

Useful starting materials are alkylated ben- R zenes, toluenes, and xylenes which include n-oc- 2 1 cHlfcflzcrrcoHi-o'fi 5 tylbenzene, n-octyltoluene, n.-octylxylenes, Z-ethl 1" Z I Y ylhexylbenzene, l-methylheptyltoluene, (l,3.- di'.-. x Y methyl-l-propylbutyl)benzene, (3,5,5-trimethyl, flfi R is an alkyl ro p of eight to Sixteen hexyDbenzene, (3.5,5-trimethylhexyl)toluene,' carbon ms, X a Y ar hydrog n o methyl, (3,5,5-trimethylhexyl) xylene, nonyltoluene (the R and R." are methyl y and Z is a Saltnonyl group being from propylene trimer), decylf n n- Th e compo n s are d inbenzene, .n-dodecylbenzene, dodecyltoluene (the guishecl by good bactericidal and fu ic dal dodecyl group being from propylene tetramer). action and y t c that t y are n tphyto tetradecylbenzene, tetradecyltoluene, tetradecyl cidal when applied to living plants in dilute dimethylbenzene, pentadecylbenzene, hexadecyl--- solutions. benzene, etc. These are halomethylated with a These compounds are p p by reacting hydrogen halide and formaldehyde or paraformy1 -2-butyn -l-01-0r 4-d et y am aldehyde or with the equivalent conveniently no-2-butyne-l-0l, in the presence of such a catalyst as zinc chloride in glacial acetic acid. There are thus obtained N CH 0:0 OH OH 2 the chloromethyl or bromomethyl derivatives .of the alkyl benzenes, including the tolueneand xylene derivatives. V with an alkylbenzyl halide, The preparation of the compounds of this in- R vention is further illustrated by the following Z 5 examples, in which parts are by weight.

. 2H V E ample X Y There were mixed 22.6 parts of 4-dimethyl- The reaction is effected by mixing these two amino 2 butyne l ol, 53 parts octylbenzyl components directly or in the presence of an chlbri'dey and 120 parts of dry benzene. Themix; organic solvent, such as benzene, toluene. lsoture was Stirred and heated under reflux fol-van propyl alcohol lsopropyl ether acetomtnle, hour. Solvent was evaporated and the residue formamide, nitromethane, or the like. Heating Stripped by 't h t 100 C./10 mm. The is useful in accelerating the reaction, temperawas a glassy masse'which corresponded tures of 50 to 125 C. being generally suitable. in ,b d octylbenzyl dimethyl 4 1 1, The product isobtained as a residue, which may y' ammonium chloride This be pur.ified. by gripping extractign Similar pound had a p efiol-c effi i nt o about. "15 f 1f a ainst dianhylo o qus .aureas and .SQ m M Q. D methyland diethyl-ammobutynols are y' 'g It ave 100 'inhihilZiQI Q eermina I aYaflable tPmugh the reaction of dimethyl' 40 tion of spores of ScZerotima "fructioola and diethyl-ammopropyne and formaldehyde under Macrosporium sarcinaeforme at 0.005% dilution. the mfluence of a cPpper catalyst Page 80, It was not phytotoxic to green plants treated of fAcetylene Chemistry by J. W. Reppe, t with a 0.1% solution thereof. The product has gai igg by Meyer New good solubility in water and other solvents.

Alkylbenzyl halides are available through halopl 2 methylation of alkylbenzenes or alkylmethylbenzenes in which the alkyl group varies from eight l ggfgg fii fl ia 5:55: 8; or preferably nine carbon atoms to about 16 methylhexynmethylbenzyl bromide, and 100 carbon atoms. The alkyl group can be straight parts of acetomtrfle The mixture was Stirred or branched. Particularly useful alkyl groups are and heated under reflux f r seven hours The Obtained m propylene polymers, fractions of solvent was driven off by heating under low preswhich give gro p predominantly of 12, or 5 sure to yield a solid, which was hygroscopic and carbon atoms. The alkyl group may also be which corresponded in composition to n0nylmethylbenzyl diethyl 4-hydroxy-2-butynyl ammonium bromide. It has a phenol coeflicient of 275 against Staphylococcus aureus and 255 against Salmonella typhosa.

' f Emample 3 A solution of 34 parts of 4-dimethylamino-2- butyne-l-ol in 80 parts of dry toluene was .treated with 97 parts of 5 -dodecyl-2-n ethyl benzyl chloride. The mixtureqwasstirred and heated to 60 0., whereupon anexothermal reaction took place. The mixture was heated under reflux for an hour and allowedtto stand, over.- night. Petroleum ether was added and the solid product precipitated. It was" separated i and ex tracted with petroleum ether several times.

, Traces of solvent were removed under low .pres sure to give an almost quantitative yield of dodecylmethylbenzyl dimethyl 4hydroxy- 2 -butynyl ammonium chloride, a soft, hygroscopic under. reflux for two hours and left standing overnight. The-solvent was evaporated under reau'cedmressure. The residue'was extracted with petroleum ether and heated under reduced pressure to give an unctious solid which corresponded 40 incomposition to Y V c micsmcnnom)anocniccom N01 'Iitratable nitrogen is nil; chlorine content is 7.9% (theory;7.88%);.-- The phenol coefficient is 530 against Staphylococcus aureus and 345 against Salmonella typhosa; It gives 100% inhibitionof germination of the above test fungi at a concentration of. 0.001% and less. It is nonphytotoxic to green plants when tested at 0.1%.

In place of a pentadecylbenzyl halide there may be used hexadecylbenzyl chloride or bromide. The quaternary salt formed is a soft, waxy solid whichhas, fairly good solubility in water and is kylbenzyl groups may be introduced in the same way. When the alkyl group contains 8 to 16 carbon atoms, the compounds obtained are surface i active and highly efiective against many types of bacteria and fungi.

4 While in the above preparations the anion Z is chlorine or bromine, since the reaction involved is that between a dialkylaminobutynol and an alkylbenzyl halide; the halide may-be replaced through metathesis with other salt-forming anion, such as sulfate, thiocyanate, acetate,

phenate, and the like. In another known way of converting the halide salt to other salt the halide may be acted upon with a hydroxide or alkoxide to displace the halide and there can then be formed the desired salt by neutralization wlth'anacid.

Wecl aim;" f 1 As'new chemical substances, compounds of the formula R! RI! @ofinmozoomon wherein R is an alkyl-group of eight to sixteen carbon atoms, X and Y aremembers of the class consisting of hydrogen and. the methyl group, R and R" are alkyl groups of not over two carbon atoms, and Z is a salt-forming anion.

2. As new chemical substances, compounds of the rformula CH3 0m cmNomozoomon wherein R is an alkyl group of nine to sixteen carbon atoms.

3; As new chemical substances, compounds of the formula on, I on, CHzNHaCEC 0112011 wherein R is an alkyl group of nine to sixteen carbon atoms.

4. As a new chemical compound; nonylbenzyl dimethyl 4-hydroxy-2-butynyl ammonium chloride.

5. As a new chemical compound, dodecylbenzyl dimethyl 4-hydroxy-2-butynyl ammonium chloride.

6. As a new chemical compound, pentadecyl- 50 benzyl dimethyl 4-hydroxy-2-butynyl ammonium chloride.

'7. As a new chemical compound, nonylmethylbenzyl dimethyl 4-hydroxy-2-butynyl ammonium chloride. a powerful bactericide and fung1c1de. Other al- WILLARD J. CROXALL. SIDNEY No references cited. 

1. AS NEW CHEMICAL SUBSTANCES, COMPOUNDS OF THE FORMULA 